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KR101395707B1 - Adhesive film for semiconductor - Google Patents

Adhesive film for semiconductor Download PDF

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Publication number
KR101395707B1
KR101395707B1 KR1020110136327A KR20110136327A KR101395707B1 KR 101395707 B1 KR101395707 B1 KR 101395707B1 KR 1020110136327 A KR1020110136327 A KR 1020110136327A KR 20110136327 A KR20110136327 A KR 20110136327A KR 101395707 B1 KR101395707 B1 KR 101395707B1
Authority
KR
South Korea
Prior art keywords
semiconductor
adhesive film
curing
curing agent
film
Prior art date
Application number
KR1020110136327A
Other languages
Korean (ko)
Other versions
KR20130068889A (en
Inventor
김혜진
최재원
김지호
김진만
송규석
Original Assignee
제일모직주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 제일모직주식회사 filed Critical 제일모직주식회사
Priority to KR1020110136327A priority Critical patent/KR101395707B1/en
Priority to US13/713,679 priority patent/US9169425B2/en
Priority to TW101147518A priority patent/TWI555812B/en
Priority to CN201210548296.1A priority patent/CN103160220B/en
Publication of KR20130068889A publication Critical patent/KR20130068889A/en
Application granted granted Critical
Publication of KR101395707B1 publication Critical patent/KR101395707B1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
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Abstract

본원 발명은 아민 경화제 및 페놀 경화제를 함께 함유하는 반도체용 접착 필름으로서, 보이드 특성 및 신뢰성 물성이 우수한 접착 필름에 관한 것이다.
보다 구체적으로, 본원 발명은 경화 전과 80% 경화 후의 저장 탄성률의 비가 1.5 내지 3.0으로 그 변화율이 큰 반도체용 접착 필름으로서, 다이 접착 시에는 유연한 물성을 띠어 보이드의 발생이 적고 EMC 몰딩 시 보이드의 제거가 쉽게 이루어져 접착 계면상의 보이드 면적을 제어하고, 경화 후에는 단단한 물성을 띠어 전단 강도 및 내리플로우성이 우수하여 신뢰성 물성이 좋은, 반도체용 접착 필름에 관한 것이다.The present invention relates to an adhesive film for semiconductor which contains an amine curing agent and a phenol curing agent together, and relates to an adhesive film excellent in void characteristics and reliability properties.
More specifically, the present invention relates to a semiconductor-use adhesive film having a ratio of storage elastic modulus before curing to that after 80% curing of 1.5 to 3.0 and having a large rate of change thereof. The adhesive film for semiconductor has flexible properties during die bonding to reduce voids, Is easily formed to control the void area on the bonding interface and has a hard physical property after curing to provide excellent shear strength and bottom flowability and good reliability properties.

Description

반도체용 접착 필름{Adhesive film for semiconductor}Adhesive film for semiconductor [

본원 발명은 아민 경화제 및 페놀 경화제를 함께 함유하는 반도체용 접착 필름으로서, 보이드 특성 및 신뢰성 물성이 우수한 접착 필름에 관한 것이다.The present invention relates to an adhesive film for semiconductor which contains an amine curing agent and a phenol curing agent together, and relates to an adhesive film excellent in void characteristics and reliability properties.

보다 구체적으로, 본원 발명은 경화 전과 80% 경화 후 170℃에서의 저장 탄성률의 비가 1.5 내지 3.0으로 큰 변화율을 나타내는 반도체용 필름으로서, 다이 접착 시에는 유연한 물성을 띠어 보이드의 발생이 적고 EMC 몰딩 시 보이드의 제거가 쉽게 이루어져 접착 계면상의 보이드 면적을 제어하고, 경화 후에는 단단한 물성을 띠어 전단 강도 및 내리플로우성이 우수하여 신뢰성 물성이 좋은, 반도체용 접착 필름에 관한 것이다.
More specifically, the present invention relates to a film for semiconductor which exhibits a large change ratio of the storage elastic modulus at 170 DEG C before curing and after storage at 170 DEG C of from 1.5 to 3.0, which exhibits flexible properties at the time of die bonding, The voids can be easily removed to control the void area on the bonding interface, and after the curing, the adhesive layer has a hard physical property and is excellent in shear strength and flowability, and thus has good reliability properties.

최근 반도체 소자의 소형화 또는 대용량화의 경향에 따라 반도체 소자와 소자, 또는 반도체 소자와 지지 부재의 접합에 접착 필름이 사용되고 있다. 반도체 조립에 사용되는 접착 필름은 다이싱(dicing) 공정에서 반도체 웨이퍼를 고정시키기 위해 사용되는 다이싱 필름과 함께 사용된다.BACKGROUND ART [0002] In recent years, an adhesive film has been used for joining semiconductor elements and devices, or semiconductor elements and supporting members, in accordance with the tendency of miniaturization or large capacity of semiconductor elements. The adhesive film used in semiconductor assembly is used with a dicing film used to fix a semiconductor wafer in a dicing process.

반도체 웨이퍼(wafer)의 조립 공정은 다이싱 필름과 접착 필름을 마운팅하고, 다이싱 공정을 통해 반도체 웨이퍼를 조각화한 다음, 다이 접착(die attach) 공정을 통해 고온 조건에서 적층시킨다. 상기 적층된 칩을 고정시키기 위해 125℃ 내지 150℃에서 일정 시간 동안 선경화(pre-cure) 공정을 거치게 되며 적층이 완료된 반도체 소자는 EMC(Epoxy Molding Compound) 몰딩 과정을 거치게 된다.
The assembly process of the semiconductor wafer mounts the dicing film and the adhesive film, and the semiconductor wafer is diced through the dicing process and then laminated at a high temperature condition through a die attach process. In order to fix the stacked chips, a pre-cure process is performed at 125 ° C to 150 ° C for a predetermined time, and the laminated semiconductor device is subjected to an epoxy molding compound (EMC) molding process.

한편, 반도체 웨이퍼가 적층되는 회로 기판에는 배선에 의한 요철이 존재하여 다이 접착 공정 중 다이와 접착제 사이의 접착 계면에 보이드(void)가 발생할 수 있으며, 칩과 칩 사이의 접착 계면 역시 보이드가 생길 수 있다. 다이 접착면에 보이드가 다량 발생하는 경우 접착 강도가 약해지고 열과 전기 전도성이 저하되게 되며 다이 크랙킹(die cracking)을 유발하는 등, 디바이스의 질과 신뢰성에 악영향을 미칠 수 있다. On the other hand, a circuit board on which semiconductor wafers are stacked has irregularities due to wiring, voids may be generated at the bonding interface between the die and the adhesive during the die bonding process, and voids may also be formed at the bonding interface between the chip and the chip . When a large amount of voids are generated on the die bonding surface, the bonding strength is weakened, heat and electric conductivity are lowered, and die cracking is caused, which may adversely affect the quality and reliability of the device.

이러한 문제점을 해결하기 위하여 유동성이 높은 접착 필름을 사용하는 경우 다이 접착 공정에서 보이드의 발생을 줄일 수 있으나, 전단 강도가 약하여 공정성이 떨어지는 문제가 있고, 모듈러스(modulus)가 높은 접착 필름을 사용하는 경우 전단 강도는 우수하나, 다이 접착 공정에서는 물론 EMC 몰딩 공정에서도 보이드를 쉽게 제거할 수 없는 문제가 있다.
In order to solve this problem, when a highly fluid adhesive film is used, the generation of voids in the die bonding process can be reduced. However, there is a problem that the shear strength is weak and the processability is poor. In the case of using an adhesive film having a high modulus The shear strength is excellent, but voids can not be easily removed in the die bonding process as well as the EMC molding process.

종래 DAF(Die attach film) 조성물로서 아크릴 바인더와 페놀 경화제가 많이 사용되어 왔으나(대한민국공개특허 제10-2009-0103434호, 대한민국등록특허 제10-0942356호 등), 상기 페놀 경화 시스템의 경우 보이드의 제거가 원활하지 않을 뿐만 아니라 경화물의 모듈러스 및 전단 강도가 낮게 나타나 신뢰성 물성이 상당히 떨어지는 문제가 있다.
Acrylic binders and phenolic curing agents have been widely used as DAF (Die attach film) compositions (Korean Patent Laid-Open No. 10-2009-0103434, Korean Patent No. 10-0942356, etc.) The removal is not smooth, and the modulus and shear strength of the cured product are low, resulting in a problem that reliability properties are significantly lowered.

이에, 다이 접착 공정 시 보이드가 적게 발생하고 이미 발생된 보이드는 EMC 몰딩 시 원활하게 제거할 수 있으면서도 전단 강도가 우수한 접착 필름의 개발이 요구되고 있는 실정이다.
Accordingly, there is a need to develop an adhesive film having a low shear strength, while voids are small in the die bonding step and voids that have already been generated can be smoothly removed during EMC molding.

대한민국공개특허공보 A 제10-2009-0103434호(2009.10.01.공개)Korean Patent Application Publication No. 10-2009-0103434 (published on October 1, 2009) 대한민국등록특허공보 B1 제10-0942356호(2010.02.12.공고)Korean Registered Patent Publication B1 10-0942356 (published on Feb. 12, 2010)

본 발명자들은 종래 반도체용 접착 필름의 문제인 접착 계면상에 보이드가 다량 발생하는 문제 및 낮은 전단 강도로 외부의 충격에 약하여 신뢰성이 떨어지는 문제를 해결하고자, 접착 필름의 제조시 아민 경화제와 페놀 경화제를 적절한 비율로 함께 사용함으로써 보이드 특성 및 신뢰성 물성이 모두 우수한 반도체용 접착 필름을 개발하기에 이르렀다.
The present inventors have intensively studied to solve the problem that a large amount of voids are generated on the bonding interface which is a problem of the conventional adhesive film for semiconductors and the problem that the reliability is weak due to external impact due to low shear strength and that the amine curing agent and phenol curing agent The present inventors have come to develop adhesive films for semiconductors having both excellent void properties and reliable physical properties.

본원 발명은 경화 전과 80% 경화 진행 후 170℃에서의 저장 탄성률의 비가 1.5 내지 3.0으로 큰 변화율을 나타내는 반도체용 접착 필름을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a semiconductor-use adhesive film which exhibits a large change ratio of storage elastic modulus at 170 占 폚 between 1.5 and 3.0 after curing and after 80% curing.

보다 구체적으로, 본원 발명은 다이 접착 시에는 유연한 물성을 띠어 보이드의 발생이 적고 EMC 몰딩 시 보이드의 제거가 쉽게 이루어져 접착 계면상의 보이드 면적을 제어하고, 경화 후에는 단단한 물성을 띠어 전단 강도 및 내리플로우성이 우수하여 신뢰성 물성이 좋은, 반도체용 접착 필름을 제공하는 것을 목적으로 한다.
More specifically, the present invention is characterized in that when the die is bonded, the voids are less likely to occur due to flexible properties, and voids can be easily removed during EMC molding to control the void area on the adhesive interface, and after hardening, And an adhesive film for semiconductors excellent in reliability and physical properties.

본원 발명은 아민 경화제 및 페놀 경화제를 함께 함유하는 반도체용 접착 필름으로서,The present invention relates to an adhesive film for semiconductor containing an amine curing agent and a phenol curing agent together,

경화 전 40℃에서의 저장 탄성률(a)과, 80% 이상 경화 진행 후 170℃에서의 저장 탄성률(b)의 비(b/a)가 1.5 내지 3.0;(B / a) of the storage modulus (a) at 40 ° C before curing and the storage modulus (b) at 170 ° C after curing at 80% or more is 1.5 to 3.0;

경화 후 저장 탄성률이 5.0(106 dyne/cm2) 이상;A storage modulus after curing of 5.0 (10 6 dyne / cm 2 ) or more;

경화 후 전단 강도가 9 kgf 이상; 및/또는Shear strength after curing is not less than 9 kgf; And / or

상기 접착 필름이 부착된 면적을 기준으로, 몰딩 후 보이드 면적이 5% 이하;인 특성을 갖는, 반도체용 접착 필름을 제공한다.
Wherein the void area after molding is 5% or less based on the area of the adhesive film.

본원 발명의 일 양태는,According to one aspect of the present invention,

아민 경화제 및 페놀 경화제를 함유하는 반도체용 접착 필름으로서,An adhesive film for semiconductor comprising an amine curing agent and a phenol curing agent,

경화 전 40℃에서의 저장 탄성률(a); 및(A) the storage elastic modulus at 40 占 폚 before curing; And

125℃에서 1시간 및 150℃에서 10분간 경화하는 것을 1 사이클로 했을 때, 총 4 사이클 진행 후 170℃에서의 저장 탄성률(b);The storage elastic modulus (b) at 170 ° C after a total of four cycles when the curing was performed at 125 ° C for 1 hour and at 150 ° C for 10 minutes as one cycle;

의 비(b/a)가 1.5 내지 3.0인, 반도체용 접착 필름을 제공한다.
(B / a) of 1.5 to 3.0.

본원 발명의 또 다른 일 양태에 따르면, 상기 아민 경화제가 디아미노 디페닐 설폰(Diamino diphenyl sulfone)인, 반도체용 접착 필름을 제공한다.According to another aspect of the present invention, there is provided an adhesive film for semiconductor, wherein the amine curing agent is diamino diphenyl sulfone.

본원 발명의 또 다른 일 양태에 따르면, 상기 페놀 경화제가 비스페놀 A 또는 비스페놀 F인, 반도체용 접착 필름을 제공한다.According to another embodiment of the present invention, there is provided an adhesive film for semiconductors, wherein the phenol hardener is bisphenol A or bisphenol F.

본원 발명의 또 다른 일 양태에 따르면, 상기 필름은 125℃에서 1시간, 150℃에서 10분 및 175℃에서 1시간 경화 후의 전단 강도(Die shear strength)가 9 kgf 이상인, 반도체용 접착 필름을 제공한다.
According to another aspect of the present invention, there is provided an adhesive film for semiconductor, wherein the film has a die shear strength of 9 kgf or more after curing at 125 ° C for 1 hour, 150 ° C for 10 minutes, and 175 ° C for 1 hour do.

본원 발명의 또 다른 일 양태에 따르면,According to another aspect of the present invention,

상기 필름이 부착된 면적을 기준으로,Based on the area of the film attached,

125℃에서 1시간 및 150℃에서 1시간 경화한 후, 175℃에서 60초간 몰딩(molding)한 뒤 175℃에서 1시간 몰드 경화 후의 보이드(void) 면적이 5% 이하인, 반도체용 접착 필름을 제공한다.
The adhesive film for semiconductor is provided with a void area of 5% or less after mold curing at 175 ° C for 1 hour after molding at 125 ° C for 1 hour and at 150 ° C for 1 hour and then at 175 ° C for 60 seconds do.

본원 발명의 또 다른 일 양태에 따르면, 아민 경화제 및 페놀 경화제를 함유하는 반도체용 접착 필름으로서, 경화 후의 전단 강도가 9 kgf 이상이고, 경화 후 170℃에서의 저장 탄성률이 5.0(106 dyne/cm2) 이상인, 반도체용 접착 필름을 제공한다.According to another aspect of the present invention, there is provided an adhesive film for semiconductor comprising an amine curing agent and a phenol curing agent, wherein the adhesive film has a shear strength after curing of 9 kgf or more and a storage modulus at 170 캜 after curing of 5.0 10 6 dyne / cm 2 ) or more.

본원 발명의 또 다른 일 양태에 따르면, 상기 필름이 부착된 면적을 기준으로, 몰딩 후 보이드 면적이 5% 이하인, 반도체용 접착 필름을 제공한다.
According to still another aspect of the present invention, there is provided an adhesive film for a semiconductor, wherein the void area after molding is 5% or less based on the area where the film is adhered.

본원 발명의 또 다른 일 양태에 따르면,According to another aspect of the present invention,

a) 바인더 수지;a) a binder resin;

b) 에폭시 수지;b) an epoxy resin;

c) 충진제;c) fillers;

d) 아민 경화제; 및d) amine curing agents; And

e) 페놀 경화제를 함유하는 반도체용 접착 필름에 있어서,e) an adhesive film for semiconductor containing a phenol curing agent,

상기 페놀 경화제(x)에 대한, 상기 아민 경화제(y)의 몰%비(y/x)가 0.3 내지 10인, 반도체용 접착 필름을 제공한다.
Wherein the mole ratio (y / x) of the amine curing agent (y) to the phenol curing agent (x) is 0.3 to 10.

본원 발명의 또 다른 일 양태에 따르면, 상기 필름은 경화 전 40℃에서의 저장 탄성률(a)에 대한, 80% 경화 후 170℃에서의 저장 탄성률(b)의 비(b/a)가 1.5 내지 3.0인, 반도체용 접착 필름을 제공한다.According to still another aspect of the present invention, the film has a ratio (b / a) of the storage modulus (b) at 170 DEG C after 80% curing to a storage modulus (a) 3.0 < / RTI >

본원 발명의 또 다른 일 양태에 따르면, 상기 필름은 경화 후의 전단 강도가 9 kgf 이상인, 반도체용 접착 필름을 제공한다.
According to still another aspect of the present invention, there is provided an adhesive film for a semiconductor, wherein the film has a shear strength of 9 kgf or more after curing.

본원 발명의 또 다른 일 양태에 따르면, 상기 필름의 고형분 100 중량부에 대하여,According to still another embodiment of the present invention,

a) 바인더 수지 40 내지 80 중량부;a) 40 to 80 parts by weight of a binder resin;

b) 에폭시 수지 1 내지 30 중량부;b) 1 to 30 parts by weight of an epoxy resin;

c) 충진제 1 내지 30 중량부;c) 1 to 30 parts by weight of a filler;

d) 아민 경화제 0.1 내지 20 중량부; 및d) 0.1 to 20 parts by weight of an amine curing agent; And

e) 페놀 경화제 0.1 내지 20 중량부e) 0.1 to 20 parts by weight of phenol curing agent

를 함유하는, 반도체용 접착 필름을 제공한다.
And an adhesive film for semiconductor.

본원 발명의 또 다른 일 양태에 따르면, 상기 바인더 수지가 엘라스토머 수지인, 반도체용 접착 필름을 제공한다.
According to still another aspect of the present invention, there is provided an adhesive film for a semiconductor, wherein the binder resin is an elastomer resin.

본원 발명의 또 다른 일 양태에 따르면, 배선 기판 및 반도체 칩을 포함하며 상기의 반도체용 접착 필름으로 접속된 반도체 장치를 제공한다.
According to another aspect of the present invention, there is provided a semiconductor device including a wiring board and a semiconductor chip and connected with the adhesive film for semiconductor.

본원 발명의 반도체용 접착 필름은 접착 계면상의 보이드 발생이 적고, 전단 강도 및 내리플로우성이 우수하여 신뢰성 물성이 높은 효과를 갖는다.The adhesive film for semiconductor of the present invention has a low occurrence of voids on the bonding interface, excellent shear strength and low flowability, and has high reliability properties.

보다 구체적으로, 본원 발명은 아민 경화제와 페놀 경화제를 함께 사용하여 경화 전(a)과 경화 후(b)의 저장 탄성률의 비(b/a)가 1.5 내지 3.0으로 그 변화율이 큰 반도체용 접착 필름으로서, 다이 접착 시에는 유연한 물성을 띠어 보이드 발생이 적고 이미 발생된 보이드의 경우 EMC 몰딩 시 쉽게 제거되어 보이드 특성이 우수하면서도, 경화 후에는 단단한 물성을 띠어 전단 강도 및 내리플로우성이 우수하여 신뢰성 물성이 좋은 반도체용 접착 필름을 제공하는 효과를 갖는다.
More specifically, the present invention relates to a process for producing a semiconductor-use adhesive film (a) for use with an amine curing agent and a phenol curing agent, wherein the ratio (b / a) of the storage modulus before curing (a) . When the die is adhered, it has flexible properties and less void formation. In the case of voids already formed, the voids are easily removed by molding, and the void properties are excellent. However, after hardening, they have a hard property and have excellent shear strength and flowability. It has an effect of providing a good adhesive film for semiconductors.

이하, 본원 발명에 대하여 보다 상세히 설명한다. 본원 명세서에 기재되지 아니한 사항은 본원 발명의 기술 분야 또는 유사 분야에서 숙련된 자이면 충분히 인식하고 유추할 수 있는 것이므로 그 설명을 생략한다.
Hereinafter, the present invention will be described in more detail. Those skilled in the art will appreciate that those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

본원 발명의 반도체용 접착 필름은 고분자 수지, 에폭시 수지, 경화제, 충진제 및 기타 첨가제가 함유될 수 있다. 이들의 종류 및 함량은 특별히 한정되지 아니하며 당해 기술 분야에서 알려진 조성을 따를 수 있다. 이하, 본원 발명의 접착 필름에 사용 가능한 성분의 구체적인 예를 기술한다.
The adhesive film for semiconductor of the present invention may contain a polymer resin, an epoxy resin, a curing agent, a filler, and other additives. The kind and content thereof are not particularly limited and may be a composition which is known in the art. Specific examples of the components usable in the adhesive film of the present invention will be described below.

고분자 수지Polymer resin

본원 발명에 사용되는 고분자 수지는 당해 기술 분야에서 통상 사용되는 것이면 그 종류가 특별히 제한되지 않는다. 상기 고분자 수지의 비제한적인 예로는 폴리이미드 수지, 폴리스타이렌 수지, 폴리에틸렌 수지, 폴리에스테르 수지, 폴리아미드 수지, 부타디엔 고무, 아크릴 고무, (메타)아크릴 수지, 우레탄 수지, 폴리페닐렌 에테르 수지, 폴리 에테르 이미드 수지, 페녹시 수지, 폴리카보네이트 수지, 폴리페닐렌 에테르 수지, 변성 폴리페닐렌 에테르 수지 및 이들의 혼합물 등을 들 수 있다. 이들은 단독 또는 2 종 이상을 혼합하여 사용할 수 있다.The type of polymer resin used in the present invention is not particularly limited as long as it is commonly used in the art. Non-limiting examples of the polymer resin include polyimide resin, polystyrene resin, polyethylene resin, polyester resin, polyamide resin, butadiene rubber, acrylic rubber, (meth) acrylic resin, urethane resin, polyphenylene ether resin, polyether Imide resins, phenoxy resins, polycarbonate resins, polyphenylene ether resins, modified polyphenylene ether resins, and mixtures thereof. These may be used alone or in combination of two or more.

또한, 관능성 모노머를 포함하는 고분자 성분, 예를 들어 글리시딜 아크릴레이트 또는 글리시딜 메타크릴레이트 등의 관능성 모노머를 함유하는 에폭시기 함유 (메타)아크릴 공중합체를 사용할 수 있다. 상기 에폭시기 함유 (메타)아크릴 공중합체로는 (메타)아크릴 에스테르 공중합체, 아크릴 고무 등을 사용할 수 있다. 이들은 단독 또는 2 종 이상을 혼합하여 사용할 수 있다.
Further, an epoxy group-containing (meth) acrylic copolymer containing a functional monomer including a functional monomer such as glycidyl acrylate or glycidyl methacrylate can be used. As the epoxy group-containing (meth) acrylic copolymer, a (meth) acrylic ester copolymer, an acrylic rubber, or the like can be used. These may be used alone or in combination of two or more.

본원 발명에 사용되는 고분자 수지로는 바람직하게는 엘라스토머 수지를 사용할 수 있다. 상기 엘라스토머 수지는 특별히 제한되지 아니하며 당해 기술 분야에서 통상 사용되는 것을 사용할 수 있다. 상기 엘라스토머 수지의 비제한적인 예로는, 아크릴로니트릴(acrylonitrile)계, 부타디엔(butadiene)계, 스티렌(styrene)계, 아크릴(acryl)계, 이소프렌(isoprene)계, 에틸렌(ethylene)계, 프로필렌(propylene)계, 폴리우레탄계 및 실리콘(silicone)계 등을 들 수 있다. 이들은 단독 또는 2 종 이상을 혼합하여 사용할 수 있다.As the polymer resin used in the present invention, an elastomer resin can be preferably used. The above-mentioned elastomer resin is not particularly limited and those conventionally used in this technical field can be used. Non-limiting examples of the elastomer resin include acrylonitrile-based, butadiene-based, styrene-based, acryl-based, isoprene-based, ethylene- propylene-based, polyurethane-based, and silicone-based. These may be used alone or in combination of two or more.

상기 엘라스토머 수지는 바람직하게는 중량 평균 분자량이 50,000 내지 5,000,000의 범위인 것을 사용할 수 있고, 보다 바람직하게는 100,000 내지 800,000인 것을 사용할 수 있다.
The elastomer resin preferably has a weight average molecular weight in the range of 50,000 to 5,000,000, more preferably 100,000 to 800,000.

상기 고분자 수지는 반도체용 접착 필름의 고형분 100 중량부에 대하여 바람직하게는 40 내지 80 중량부로 함유될 수 있으며, 보다 바람직하게는 50 내지 70 중량부로 함유될 수 있다. 상기 범위에서 우수한 신뢰성과 보이드의 제거 효과를 얻을 수 있다.
The polymer resin may be contained in an amount of preferably 40 to 80 parts by weight, more preferably 50 to 70 parts by weight, based on 100 parts by weight of the solid content of the adhesive film for semiconductor. It is possible to obtain excellent reliability and void removal effect in the above range.

에폭시 수지Epoxy resin

본원 발명에 사용되는 에폭시 수지는 당해 기술 분야에서 통상 사용되는 것이면 그 종류가 특별히 제한되지 아니하며, 액상 에폭시 수지 또는 고상 에폭시 수지를 어느 하나 이상 포함할 수 있다.The type of the epoxy resin used in the present invention is not particularly limited as long as it is commonly used in the art, and may include at least one of a liquid epoxy resin or a solid epoxy resin.

상기 액상 에폭시 수지의 비제한적인 예로, 비스페놀 A형 액상 에폭시 수지, 비스페놀 F형 액상 에폭시 수지, 3 관능성 이상의 다관능성 액상 에폭시 수지, 고무변성 액상 에폭시 수지, 우레탄 변성 액상 에폭시 수지, 아크릴 변성 액상 에폭시 수지 및 감광성 액상 에폭시 수지 등을 들 수 있다. 이들은 단독 또는 2 종 이상을 혼합하여 사용할 수 있다.Non-limiting examples of the liquid epoxy resin include bisphenol A type liquid epoxy resin, bisphenol F type liquid epoxy resin, trifunctional or higher polyfunctional liquid epoxy resin, rubber modified liquid epoxy resin, urethane modified liquid epoxy resin, acrylic modified liquid epoxy A resin and a photosensitive liquid epoxy resin. These may be used alone or in combination of two or more.

상기 액상 에폭시 수지는 바람직하게는 에폭시 당량이 약 100 내지 약 1500 g/eq 인 것이 사용될 수 있으며, 보다 바람직하게는 약 150 내지 약 800 g/eq 인 것이 사용될 수 있고, 가장 바람직하게는 약 150 내지 약 400 g/eq 인 것이 사용될 수 있다. 상기 범위에서 경화물의 접착성이 우수하고, 높은 유리 전이 온도를 유지하며, 우수한 내열성을 가질 수 있다.The liquid epoxy resin may preferably be one having an epoxy equivalent of about 100 to about 1500 g / eq, more preferably about 150 to about 800 g / eq, and most preferably about 150 to about 800 g / About 400 g / eq can be used. Within the above range, the cured product is excellent in adhesion, can maintain a high glass transition temperature, and can have excellent heat resistance.

또한 상기 액상 에폭시 수지는 바람직하게는 중량 평균 분자량은 100 내지 1,000 g/mol 인 것이 사용될 수 있다. 상기 범위에서 흐름성이 뛰어난 장점이 있다.
The liquid epoxy resin preferably has a weight average molecular weight of 100 to 1,000 g / mol. There is an advantage in that the flowability is excellent in the above range.

상기 고상 에폭시 수지는 상온에서 고상 또는 고상에 근접한 에폭시로서 하나 이상의 관능기를 가지고 있는 에폭시 수지를 사용할 수 있으며, 그의 비제한적인 예로는, 비스페놀계 에폭시, 페놀 노볼락(phenol novolac)계 에폭시, o-크레졸 노볼락(cresol novolac)계 에폭시, 다관능 에폭시, 아민계 에폭시, 복소환 함유 에폭시, 치환형 에폭시, 나프톨계 에폭시 및 이들의 유도체등을 들 수 있다.The solid epoxy resin may be an epoxy resin having at least one functional group as a solid epoxy resin near room temperature or solid state at room temperature. Non-limiting examples of the epoxy resin include bisphenol epoxy, phenol novolac epoxy, o- Cresol novolac-based epoxy, polyfunctional epoxy, amine-based epoxy, heterocyclic-containing epoxy, substituted epoxy, naphthol-based epoxy, and derivatives thereof.

이러한 에폭시계 수지로서 현재 시판되고 있는 제품에는 비스페놀계로서는 국도 화학의 YD-017H, YD-020, YD020-L, YD-014, YD-014ER, YD-013K, YD-019K, YD-019, YD-017R, YD-017, YD-012, YD-011H, YD-011S, YD-011, YDF-2004, YDF-2001 등이 있고, 페놀 노볼락(Phenol novolac)계로서는 유카 쉘 에폭시 주식회사의 체피코트 152, 에피코트 154, 일본 화약 주식회사의 EPPN-201, 다우 케미컬의 DN-483, 국도 화학의 YDPN-641, YDPN-638A80, YDPN-638, YDPN-637, YDPN-644, YDPN-631 등이 있고, o-크레졸 노볼락(Cresol novolac)계로서는 국도 화학의 YDCN-500-1P, YDCN-500-2P, YDCN-500-4P, YDCN-500-5P, YDCN-500-7P, YDCN-500-8P, YDCN-500-10P, YDCN-500-80P, YDCN-500-80PCA60, YDCN-500-80PBC60, YDCN-500-90P, YDCN-500-90PA75 등이 있고 일본 화약 주식회사의 EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, 독도 화학 주식회사의 YDCN-701, YDCN-702, YDCN-703, YDCN-704, 대일본 잉크화학의 에피클론 N-665-EXP 등이 있고, 비스페놀계 노볼락 에폭시로는 국도 화학의 KBPN-110, KBPN-120, KBPN-115 등이 있고, 다관능 에폭시 수지로서는 유카 쉘 에폭시 주식회사 Epon 1031S, 시바 스페샬리티 케미칼 주식회사의 아랄디이토 0163, 나가섭씨온도 화성 주식회사의 데타콜 EX-611, 데타콜 EX-614, 데타콜 EX-25-12614B, 데타콜 EX-622, 데타콜 EX-512, 데타콜 EX-521, 데타콜 EX-421, 데타콜 EX-411, 데타콜 EX-321, 국도 화학의 EP-5200R, KD-1012, EP-5100R, KD-1011, KDT-4400A70, KDT-4400, YH-434L, YH-434, YH-300 등이 있으며, 아민계 에폭시 수지로서는 유카 쉘 에폭시 주식회사 에피코트 604, 독도 화학 주식회사의 YH-434, 미쓰비시가스화학 주식회사의 TETRAD-X, TETRAD-C, 스미토모 화학 주식회사의 ELM-120 등이 있고, 복소환 함유 에폭시 수지로는 시바 스페샬리티 케미칼 주식회사의 PT-810, 치환형 에폭시 수지로는 UCC사의 ERL-4234, ERL-4299, ERL-4221, ERL-4206, 나프톨계 에폭시로는 대일본 잉크화학의 에피클론 HP-4032, 에피클론 HP-4032D, 에피클론 HP-4700, 에피클론 4701 등이 있다. 이들은 단독 또는 2종 이상을 혼합하여 사용할 수 있다.YD-019, YD-019, YD-019, YD-019, YD-019K, YD-019K, YD-019K, YD- YD-017, YD-017, YD-012, YD-011H, YD-011S, YD-011, YDF-2004 and YDF- YDPN-638, YDPN-638, YDPN-637, YDPN-644, and YDPN-631 of National Chemical Industries, Ltd., and EPPN-201 of Nippon Yakusho Co., Ltd., DN-483 of Dow Chemical Co., , YCN-500-P, YDCN-500-2P, YDCN-500-4P, YDCN-500-5P, YDCN-500-7P, YDCN-500-8P , YDCN-500-80P, YDCN-500-80P, YDCN-500-80PCA60, YDCN-500-80PBC60, YDCN-500-90P and YDCN-500-90PA75. YDCN-701, YDCN-703, YDCN-704, and YDCN-704 of Dokdo Chemical Co., Ltd., EOCN-1012, EOCN-1025 and EOCN- KBPN-120, and KBPN-115, which are available from Kukdo Chemical Co., Ltd., Epon 1031S, Epa 1031S manufactured by Yucca Shell Epoxy Co., Ltd., DataColor EX-611, DataCol EX-614, DataCol EX-25-12614B, DataCol EX-622, DataCol EX-512, DataCol EX KD-4400A70, KDT-4400, YH-521, DataColor EX-421, DataColor EX-411, DataColor EX-321, EP-5200R, KD-1012, EP-5100R, KD- 434L, YH-434, and YH-300. Examples of the amine-based epoxy resin include Epikote 604 manufactured by Yuka Shell Epoxy Co., Ltd., YH-434 manufactured by Dokdo Chemical Co., Ltd., TETRAD-X and TETRAD- C manufactured by Mitsubishi Gas Chemical Co., ELM-120, and the like. Examples of the heterocyclic ring-containing epoxy resin include PT-810 of Ciba Specialty Chemicals Co., Epclone HP-4032D, Epiclon HP-4700, Epiclon 4701, and the like manufactured by Dainippon Ink and Chemicals, Inc. are used as the curing accelerators ERL-4234, ERL-4299, ERL- . These may be used alone or in combination of two or more.

상기 에폭시 수지는 반도체용 접착 필름의 고형분 100 중량부에 대하여 바람직하게는 1 내지 30 중량부로 함유될 수 있고, 보다 바람직하게는 5 내지 20 중량부로 함유될 수 있다. 상기 범위에서 우수한 신뢰성 및 보이드 제거 효과를 얻을 수 있다.
The epoxy resin may be contained in an amount of preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the solid content of the adhesive film for semiconductor. Excellent reliability and void removal effect can be obtained in the above range.

아민 경화제Amine curing agent

본원 발명에 사용되는 아민 경화제는 당해 기술 분야에서 통상 사용되는 것이면 그 종류가 특별히 제한되지 않는다.The type of amine curing agent used in the present invention is not particularly limited as long as it is usually used in the art.

상기 아민 경화제의 비제한 적인 예로는, 3,3'-디아미노벤지딘, 4,4'-디아미노디페닐 메탄, 4,4' 또는 3,3'-디아미노디페닐 설폰, 4,4'-디아미노벤조페논, 파라페닐렌 디아민, 메타페닐렌, 디아민, 메타톨루엔 디아민, 4,4'-디아미노디페닐 에테르, 4,4' 또는 3,3'-디아미노벤조페논, 1,4'또는 1,3'-비스(4 또는 3-아미노큐밀)벤젠, 1,4'-비스(4 또는 3-아미노페녹시)벤젠, 2,2'-비스[4-(4 또는 3-아미노페녹시)페닐]프로판, 비스[4-(4 또는 3-아미노페녹시)페닐]설폰, 2,2'-비스[4-(4 또는 3-아미노페녹시)페닐]헥사플루오로설폰, 2,2'-비스[4-(4 또는 3-아미노페녹시)페닐]헥사플루오로프로판, 4,4'-디아미노-3,3',5,5'-테트라부틸디페닐케톤, 4,4'-디아미노-3,3',5,5'-테트라에틸디페닐케톤, 4,4'-디아미노-3,3',5,5'-테트라-n-프로필렌디페닐케톤, 4,4'-디아미노-3,3',5,5'-테트라이소프로필디페닐케톤, 4,4'-디아미노-3,3',5,5'-테트라메틸디페닐케톤, 4,4'-디아미노-3,3',5,5'-테트라-n-프로필디페닐메탄, 4,4'-디아미노-3,3'5,5-테트라메틸디페닐메탄, 4,4'-디아미노-3,3'5,5'-테트라이소프로필디페닐메탄, 4,4'-디아미노-3,3'5,5'-테트라에틸디페닐메탄, 4,4'-디아미노-3,3'-디메틸-5,5'-디에틸디페닐메탄, 4,4'-디아미노-3,3'-디메틸-5,5'-디이소프로필디페닐메탄, 4,4'-디아미노-3,3'-디에틸-5,5'-디에틸디페닐메탄, 4,4'-디아미노-3,5'-디메틸-3',5'-디에틸디페닐메탄, 4,4'-디아미노-3,5-디메틸-3',5'-디이소프로필디페닐메탄, 4,4'-디아미노-3,5-디에틸-3',5'-디부틸디페닐메탄, 4,4'-디아미노-3,5-디이소프로필-3',5'-디부틸디페닐메탄, 4,4'-디아미노-3,3'-디이소프로필-5,5'-디부틸디페닐메탄, 4,4'-디아미노-3,3'-디메틸-5',5'-디부틸디페닐메탄, 4,4'-디아미노-3,3'-디에틸-5',5'-디부틸디페닐메탄, 4,4'-디아미노-3,3'-디메틸디페닐메탄, 4,4'-디아미노-3,3'-디에틸디페닐메탄, 4,4'-디아미노-3,3'-디-n-프로필디페닐메탄, 4,4'-디아미노-3,3'-디이소프로필디페닐메탄, 4,4'-디아미노-3,3'-디부틸디페닐메탄, 4,4'-디아미노-3,3',5-트리메틸디페닐메탄, 4,4'-디아미노-3,3',5-트리에틸디페닐메탄, 4,4'-디아미노-3,3',5-트리-n-프로필디페닐메탄, 4,4'-디아미노-3,3',5-트리이소프로필디페닐메탄, 4,4'-디아미노-3,3',5-트리부틸디페닐메탄, 4,4'-디아미노-3-메틸-3'-에틸디페닐메탄, 4,4'-디아미노-3-메틸-3'-이소프로필디페닐메탄, 4,4'-디아미노-3-메틸-3'-부틸디페닐메탄, 4,4'-디아미노-3-이소프로필-3'-부틸디페닐메탄, 2,2-비스(4-아미노-3,5-디메틸페닐)프로판, 2,2-비스(4-아미노-3,5-디에틸페닐)프로판, 2,2-비스(4-아미노-3,5-디-n-프로필페닐)프로판, 2,2-비스(4-아미노-3,5-디이소프로필페닐)프로판, 2,2-비스(4-아미노-3,5-디부필페닐)프로판, 4,4'-디아미노-3,3',5,5'-테트라메틸디페닐벤즈아닐리드, 4,4'-디아미노-3,3',5,5'-테트라에틸디페닐벤즈아닐리드, 4,4'-디아미노-3,3',5,5'-테트라-n-프로필디페닐벤즈아닐리드, 4,4'-디아미노-3,3',5,5'-테트라이소프로필디페닐벤즈아닐리드, 4,4'-디아미노-3,3',5,5'-테트라부틸디페닐벤즈아닐리드, 4,4'-디아미노-3,3',5,5'-테트라메틸디페닐설폰, 4,4'-디아미노-3,3',5,5'-테트라에틸디페닐설폰, 4,4'-디아미노-3,3',5,5'-테트라-n-프로필디페닐설폰, 4,4'-디아미노-3,3',5,5'-테트라이소프로필디페닐설폰, 4,4'-디아미노-3,3',5,5'-테트라메틸디페닐에테르, 4,4'-디아미노-3,3',5,5'-테트라에틸디페닐에테르, 4,4'-디아미노-3,3',5,5'-테트라-n-프로필디페닐에테르, 4,4'-디아미노-3,3',5,5'-테트라이소프로필디페닐에테르, 4,4'-디아미노-3,3',5,5'-테트라부틸디페닐에테르, 3,3'-디아미노벤조페논, 3,4-디아미노벤조페논, 3,3'-디아미노디페닐에테르, 3,3'-디아미노디페닐메탄, 3,4'-디아미노디페닐메탄, 2,2'-디아미노-1,2-디페닐에탄 또는 4,4'-디아미노-1,2-디페닐에탄, 2,4-디아미노디페닐아민, 4,4'-디아미노옥타플루오로바이페닐, o-디아니시딘 등을 들 수 있다. 이들은 단독 또는 2 이상을 혼합하여 사용할 수 있다.Nonlimiting examples of the amine curing agent include 3,3'-diaminobenzidine, 4,4'-diaminodiphenylmethane, 4,4 'or 3,3'-diaminodiphenylsulfone, 4,4' Diaminobenzophenone, paraphenylenediamine, metaphenylene, diamine, metatoluenediamine, 4,4'-diaminodiphenyl ether, 4,4 'or 3,3'-diaminobenzophenone, 1,4 Benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2'-bis [4- (4- or 3- (4 or 3-aminophenoxy) phenyl] hexafluorosulfone, 2, 2'-bis [4- , 4'-diamino-3,3 ', 5,5'-tetrabutyldiphenylketone, 4'-diamine, 4'- Diamino-3,3 ', 5,5'-tetraethyldiphenylketone, 4,4'-diamino-3,3', 5,5'-tetra-n-propyldiphenylketone, 4 , 4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenylketone , 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenyl ketone, 4,4'-diamino-3,3', 5,5'-tetra- Methane, 4,4'-diamino-3,3'5,5-tetramethyldiphenylmethane, 4,4'-diamino-3,3'5,5'-tetraisopropyldiphenylmethane, 4'-diamino-3,3'5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane, -Diamino-3,3'-dimethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-diethyldiphenylmethane , 4,4'-diamino-3,5'-dimethyl-3 ', 5'-diethyldiphenylmethane, 4,4'-diamino-3,5-dimethyl- Diisopropyl-3 ', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,5-diisopropyl-3' , 5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-diisopropyl-5,5'-dibutyldiphenylmethane, 4,4'- -Dimethyl-5 ', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5', 5'-dibutyldiphenylmethane, Amino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diamino-3,3'-di- Phenylmethane, 4,4'-diamino-3,3'-diisopropyldiphenylmethane, 4,4'-diamino-3,3'-dibutyldiphenylmethane, 4,4'- 3,3 ', 5-trimethyldiphenylmethane, 4,4'-diamino-3,3', 5-triethyldiphenylmethane, 4,4'- 4,4'-diamino-3,3 ', 5-triisopropyldiphenylmethane, 4,4'-diamino-3,3', 5-tributyldiphenylmethane, Diamino-3-methyl-3'-ethyldiphenylmethane, 4,4'-diamino-3-methyl-3'-isopropyldiphenylmethane, 4,4'- -Methyl-3'-butyldiphenylmethane, 4,4'-diamino-3-isopropyl-3'-butyldiphenylmethane, 2,2- , 2,2-bis (4-amino-3,5-diethylphenyl) propane, 2,2- 4-amino-3,5-diisopropylphenyl) propane, 2, Bis (4-amino-3,5-di-biphenyl) propane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylbenzanilide, 3,3 ', 5,5'-tetra-n-propyldiphenylbenzanilide, 4,4'-diamino-3,3' -Diamino-3,3 ', 5,5'-tetraisopropyldiphenylbenzanilide, 4,4'-diamino-3,3', 5,5'-tetrabutyldiphenylbenzanilide, Diamino-3,3 ', 5,5'-tetramethyldiphenylsulfone, 4,4'-diamino-3,3', 5,5'-tetraethyldiphenylsulfone, 4,4'- Diamino-3,3 ', 5,5'-tetra-n-propyldiphenylsulfone, 4,4'-diamino-3,3', 5,5'-tetraisopropyldiphenylsulfone, Diamino-3,3 ', 5,5'-tetramethyldiphenyl ether, 4,4'-diamino-3,3', 5,5'-tetraethyldiphenyl ether, 4,4'- Diamino-3,3 ', 5,5'-tetra-n-propyl diphenyl ether, 4,4'-diamino-3,3', 5,5'-tetraisopropyl diphenyl ether, '-Diamino-3,3', 5,5'-tetrabutyldiphe Ether, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diamino Diphenylmethane, 2,2'-diamino-1,2-diphenylethane or 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylamine, 4,4 ' - diamino octafluorobiphenyl, o-dianisidine and the like. These may be used singly or in combination of two or more.

상기 아민 경화제로는 바람직하게는 디아미노 디페닐 설폰을 사용할 수 있다.The amine curing agent is preferably diaminodiphenylsulfone.

상기 아민 경화제는 반도체용 접착 필름의 고형분 100 중량부에 대하여 바람직하게는 0.1 내지 20 중량부로 함유될 수 있고, 보다 바람직하게는 1 내지 10 중량부로 함유될 수 있다. 상기 범위 내에서 보이드 발생 억제 및 몰딩 시 원활한 보이드 제거 효과를 얻을 수 있다.
The amine curing agent may be contained in an amount of preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the solid content of the adhesive film for semiconductor. It is possible to suppress void formation within the above range and to obtain a smooth void removal effect upon molding.

페놀 경화제Phenol hardener

본원 발명에 사용되는 페놀 경화제는 당해 기술 분야에서 통상 사용되는 것이면 그 종류가 특별히 제한되지 않는다.The type of phenolic curing agent used in the present invention is not particularly limited as long as it is usually used in the art.

상기 페놀 경화제의 비제한적인 예로는, 비스페놀 A, 비스페놀 F, 비스페놀 S 등의 비스페놀계 수지; 페놀 노볼락계 수지; 비스페놀 A계 노볼락 수지; 자일록계, 크레졸계 노볼락, 비페닐계 등의 페놀계 수지 등을 들 수 있다.Non-limiting examples of the phenol curing agent include bisphenol-based resins such as bisphenol A, bisphenol F, and bisphenol S; Phenol novolac resins; Bisphenol A novolac resins; Phenolic resins such as xylyl type resins, cresol type novolac resins and biphenyl type resins.

이러한 페놀 경화제로서 현재 시판되고 있는 제품의 예로는, 단순 페놀계의 경화제로 메이화 플라스틱 산업 주식회사의 H-1, H-4, HF-1M, HF-3M, HF-4M, HF-45 등이 있고, 파라 자일렌계열의 메이화 플라스틱 산업 주식회사의 MEH-78004S, MEH-7800SS, MEH-7800S, MEH-7800M, MEH-7800H, MEH-7800HH, MEH-78003H, 코오롱 유화 주식회사의 KPH-F3065, 비페닐 계열의 메이화 플라스틱 산업 주식회사의 MEH-7851SS, MEH-7851S, MEH7851M, MEH-7851H, MEH-78513H, MEH-78514H, 코오롱 유화 주식회사의 KPH-F4500, 트리페닐메틸계의 메이화 플라스틱 산업 주식회사의 MEH-7500, MEH-75003S, MEH-7500SS, MEH-7500S, MEH-7500H 등이 있다. 이들은 단독 또는 2종 이상을 혼합하여 사용할 수 있다.H-1, H-4, HF-1M, HF-3M, HF-4M, and HF-45 of Meiwa Plastic Industries, Ltd. are used as a simple phenol type hardening agent. MEH-7800H, MEH-7800H, MEH-78003H, Kolon Kikai KKHH-F3065, MEH-78004S, MEH-7800SS, MEH-7800S, MEH-7851S, MEH7851M, MEH-7851H, MEH-78513H, MEH-78514H from Kolmar Chemical Industries, Ltd., KPH-F4500 from Kolon Chemical Industries Co., Ltd., MEH-7500S, MEH-7500S, MEH-7500S, and MEH-7500H. These may be used alone or in combination of two or more.

상기 페놀 경화제로 바람직하게는 당량이 100 내지 150 g/eq인 비스페놀 A 또는 비스페놀 F를 사용할 수 있다.As the phenol hardener, bisphenol A or bisphenol F having an equivalent weight of 100 to 150 g / eq can be used.

상기 페놀 경화제는 반도체용 접착 필름의 고형분 100 중량부에 대하여 바람직하게는 0.1 내지 20 중량부로 함유될 수 있으며 보다 바람직하게는 1 내지 10 중량부로 함유될 수 있다. 상기 범위를 벗어나면 접착제로서의 접착성과 경화성이 떨어지는 경향이 있으며, 상기 범위 내에서 보이드 발생 억제 및 몰딩 시 원활한 보이드 제거 효과를 얻을 수 있다.
The phenolic curing agent may be contained in an amount of preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the solid content of the adhesive film for semiconductor. Outside of the above range, adhesiveness as an adhesive agent and curability tends to deteriorate, and it is possible to suppress the generation of voids within the above range and to obtain a smooth void removal effect upon molding.

상기 페놀 경화제(x)에 대한, 상기 아민 경화제(y)의 몰%비(y/x)는 바람직하게는 0.3 내지 10일 수 있으며, 보다 바람직하게는 0.5 내지 10일 수 있다. 상기 몰%비가 10을 초과할 경우에는 아민 경화제에 대한 페놀 경화제의 산촉매적 반응이 잘 이루어지지 않아 경화 반응 속도가 지나치게 느려질 수 있으며, 0.3 미만일 경우에는 아민 경화제의 함량이 부족하여 몰딩 시 원활한 보이드 제거 효과를 충분히 얻을 수 없는 문제가 발생할 우려가 있다.
The mole% ratio (y / x) of the amine curing agent (y) to the phenolic curing agent (x) may be preferably 0.3 to 10, more preferably 0.5 to 10. If the mole% ratio is more than 10, the reaction of the phenol hardener with the amine hardener may not be performed well and the rate of the hardening reaction may be too slow. If the molar ratio is less than 0.3, the content of the amine hardener may be insufficient, There is a possibility that a problem that the effect can not be sufficiently obtained may occur.

충진제Filler

본원 발명의 접착 조성물은 틱소트로픽성(thixotropy)을 발현하여 용융점도를 조절하기 위하여 충진제를 포함할 수 있다. 상기 충진제는 당해 기술 분야에서 통상 사용되는 것이면 그 종류가 특별히 제한되지 않는다. 상기 충진제로는 필요에 따라 무기 또는 유기 충진제를 사용할 수 있으며, 무기 충진제로는 금속성분인 금가루, 은가루, 동분, 니켈을 사용할 수 있고, 비금속성분인 알루미나, 수산화 일미늄, 수산화 마그네슘, 탄산칼슘, 탄산마그네슘, 규산칼슘, 규산마그네슘, 산화칼슘, 산화마그네슘, 산화 알루미늄, 질화 알루미늄, 실리카, 질화 붕소, 이산화티타늄, 유리, 산화철, 세라믹 등을 사용할 수 있고, 유기 충진제로서는 카본, 고무계 필러, 폴리머계 등을 사용할 수 있다. 상기 충진제의 형상과 크기는 특별히 제한되지 아니하나, 바람직하게는 구형일 수 있으며 크기는 500 nm 내지 10 ㎛의 범위가 바람직하다.
The adhesive composition of the present invention may contain a filler to control thixotropy and control melt viscosity. The kind of the filler is not particularly limited as long as it is commonly used in the art. As the inorganic filler, gold powder, silver powder, copper powder, and nickel, which are metal components, may be used. As the inorganic filler, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, Silica, boron nitride, titanium dioxide, glass, iron oxide, ceramics and the like can be used. As the organic filler, there can be used carbon, rubber fillers, polymeric fillers such as calcium carbonate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, silica, Etc. may be used. The shape and size of the filler are not particularly limited, but may preferably be spherical and the size is preferably in the range of 500 nm to 10 mu m.

상기 충진제의 형상 및 크기는 특별히 제한되지 아니하며 당해 기술 분야에서 통상 사용되는 것을 사용할 수 있으나, 바람직하게는 5 nm 내지 20 ㎛ 크기의 구형 실리카를 사용할 수 있다.The shape and size of the filler are not particularly limited and those generally used in the art may be used, but spherical silica having a size of 5 nm to 20 탆 may be preferably used.

상기 충진제는 반도체용 접착 필름의 고형분 100 중량부에 대하여 바람직하게는 1 내지 30 중량부로 함유될 수 있고, 보다 바람직하게는 5 내지 20 중량부로 함유될 수 있다. 상기 충진제의 함량이 1 중량부 미만일 경우에는 충진제 첨가에 의한 보강 효과가 작아지고, 30 중량부를 초과하는 경우에는 피착제에 대한 접착성이 저하될 우려가 있다. 상기 범위에서 우수한 유동성과 필름 형성성 및 접착성을 가질 수 있다.
The filler may be contained in an amount of preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the solid content of the adhesive film for semiconductor. When the content of the filler is less than 1 part by weight, the reinforcing effect by the addition of the filler is small. When the content of the filler exceeds 30 parts by weight, there is a fear that the adhesion to the adherend is lowered. And can have excellent flowability, film formability and adhesiveness in the above range.

실란Silane 커플링제Coupling agent

본원 발명에 사용되는 커플링제는 조성물 배합시 실리카와 같은 무기물질의 표면과 유기 물질간의 화학적 결합으로 인한 접착력을 증진시키기 위한 접착증진제의 작용을 한다.The coupling agent used in the present invention acts as an adhesion promoter for improving the adhesion due to the chemical bonding between the surface of the inorganic material such as silica and the organic material when the composition is formulated.

상기 커플링제는 당해 기술 분야에서 통상 사용되는 것이면 그 종류가 특별히 제한되지 아니하며, 그 비제한적인 예로는, 에폭시가 함유된 2-(3,4 에폭시 사이클로 헥실)-에틸트리메톡시실란, 3-글리시독시트리메톡시실란, 3-글리시독시프로필트리에톡시실란, 아민기가 함유된 N-2(아미노에틸)3-아미토프로필메틸디메톡시실란, N-2(아미노에틸)3-아미노프로필트리메톡시실란, N-2(아미노에틸)3-아미노프로필트리에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-트리에톡시실리-N-(1,3-디메틸뷰틸리덴)프로필아민, N-페닐-3-아미노프로필트리메톡시실란, 머캅토가 함유된 3-머캅토프로필메틸디메톡시실란, 3-머캅토프로필트리에톡시실란, 이소시아네이트가 함유된 3-이소시아네이트프로필트리에톡시실란 등을 들 수 있다. 이들을 단독 또는 2종 이상을 혼합하여 사용할 수 있다.The coupling agent is not particularly limited as long as it is commonly used in the art. Non-limiting examples of the coupling agent include 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane containing epoxy, 3- Glycidoxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane containing an amine group, N-2 (aminoethyl) 3-amino Aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (2-aminopropyltriethoxysilane, 1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, mercapto-containing 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, And 3-isocyanate propyltriethoxysilane containing isocyanate. These may be used singly or in combination of two or more.

상기 커플링제는 반도체용 접착 필름의 고형분 100 중량부에 대하여 바람직하게는 0.01 내지 10 중량부로 함유될 수 있고, 보다 바람직하게는 0.1 내지 5 중량부로 함유될 수 있다. 상기 범위에서 우수한 접착 신뢰성을 얻을 수 있고 버블 발생을 줄일 수 있다.
The coupling agent may be contained in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the solid content of the adhesive film for semiconductor. Excellent adhesion reliability can be obtained within the above range and bubble generation can be reduced.

경화 촉매Curing catalyst

본원 발명에 사용되는 상기 경화 촉매는 반도체 공정 동안에 에폭시 수지가 완전히 경화될 수 있도록 경화시간을 단축시키는 촉매로서, 당해 기술 분야에서 통상 사용되는 것이면 그 종류가 특별히 제한되지 않는다. 상기 경화 촉매의 비제한적인 예로는 멜라민계, 이미다졸계, 트리페닐포스핀계 촉매 등을 들 수 있다. 현재 시판되고 있는 제품의 예로는, 이미다졸계로서 아지노모토 정밀 기술 주식회사의 PN-23, PN-40, 사국 화학 주식회사의 2P4MZ, 2MA-OK, 2MAOK-PW, 2P4MHZ 등이 있고, 호코 케미칼사(HOKKO CHEMICAL INDUSTRY CO., LTD)의 TPP-K, TPP-MK 등이 있다. 이들은 단독 또는 2종 이상을 혼합하여 사용할 수 있다.The curing catalyst used in the present invention is a catalyst for shortening the curing time so that the epoxy resin can be completely cured during the semiconductor process, and the kind thereof is not particularly limited as long as it is commonly used in the art. Non-limiting examples of the curing catalyst include melamine-based, imidazole-based, and triphenylphosphine-based catalysts. 2M-OK, 2MAOK-PW, and 2P4MHZ of Ajinomoto Precision Technology Co., Ltd., PNK-23, PN-40, and Sankoku Chemical Co., Ltd. as the imidazole system. HOKKO CHEMICAL INDUSTRY CO., LTD.) TPP-K and TPP-MK. These may be used alone or in combination of two or more.

상기 경화 촉매는 반도체용 접착 필름의 고형분 100 중량부에 대하여 바람직하게는 0.01 내지 10 중량부로 함유될 수 있고, 보다 바람직하게는 0.03 내지 5 중량부로 함유될 수 있다. 상기 경화 촉매의 함량이 0.01 중량부 미만일 경우에는 에폭시 수지의 가교가 불충분하게 되고 내열성이 저하될 우려가 있으며, 10 중량부를 초과하는 경우에는 보존 안정성이 저하될 우려가 있다.
The curing catalyst may be contained in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the solid content of the adhesive film for semiconductor. When the content of the curing catalyst is less than 0.01 part by weight, crosslinking of the epoxy resin becomes insufficient and there is a fear that the heat resistance is lowered. When it exceeds 10 parts by weight, there is a fear that the storage stability is lowered.

이온 ion 포착제Capture agent

한편, 본원 발명의 반도체용 접착 필름을 제조하는 데에 있어서 이온성 불순물을 흡착하고 흡습 시의 절연 신뢰성을 구현하기 위하여 이온 포착제를 추가로 사용할 수 있다. 상기 이온 포착제로는 당해 기술 분야에서 통상 사용되는 것이면 그 종류가 특별히 제한되지 아니하며, 비제한적인 예로 트리아진 티올(Triazin thiol)화합물, 지르코늄계(Zirconium), 안티몬 비스무트계(Antimon bismuth), 마그네슘 알루미늄계(magnesium aluminium) 화합물 등을 들 수 있다.
On the other hand, in the production of the adhesive film for semiconductor of the present invention, an ion trapping agent may be further added to adsorb ionic impurities and realize insulation reliability at the time of moisture absorption. The ion trapping agent is not particularly limited as long as it is commonly used in the art, and examples thereof include, but not limited to, triazin thiol compounds, zirconium, antimony bismuth, magnesium aluminum Magnesium aluminum compounds and the like.

유기 용매Organic solvent

본원 발명의 반도체용 접착 필름을 제조하는 데에 있어서 유기용매를 사용할 수 있다. 상기 유기용매는 반도체용 접착 조성물의 점도를 낮게 하여 필름의 제조가 용이하도록 하며, 당해 기술 분야에서 통상 사용되는 것이면 그 종류가 특별히 제한되지 않는다. 그 비제한적인 예로는, 톨루엔, 자일렌, 프로필렌 글리콜 모노메틸 에테르 아세테이트, 벤젠, 아세톤, 메틸에틸케톤, 테트라히드로 퓨란, 디메틸포름알데히드, 시클로헥사논 등을 들 수 있다.
An organic solvent may be used in the production of the adhesive film for semiconductor of the present invention. The organic solvent lowers the viscosity of the adhesive composition for semiconductor to facilitate the production of the film. The type of the organic solvent is not particularly limited as long as it is usually used in the art. Non-limiting examples thereof include toluene, xylene, propylene glycol monomethyl ether acetate, benzene, acetone, methyl ethyl ketone, tetrahydrofuran, dimethyl formaldehyde, cyclohexanone and the like.

본원 발명의 반도체용 접착 필름은 그 필름을 형성하는 데에 특별한 장치나 설비가 필요치 아니하며, 당해 기술 분야에서 알려진 방법에 의해 특별한 제한없이 제조될 수 있다.The adhesive film for semiconductor of the present invention does not require any special apparatus or equipment for forming the film, and can be manufactured without any particular limitation by a method known in the art.

반도체용 접착 필름을 제조하는 방법의 비제한적인 예는 다음과 같다: 상기 제시된 각 성분을 용매에 용해시킨 후 비즈밀을 이용하여 충분히 혼련시킨 다음, 어플리케이터를 이용하여 이형 처리된 폴리에틸렌 테레프탈레이트(PET) 필름상에 도포하고 100℃ 오븐에서 약 10 내지 30분 동안 가열 건조하여 적당한 도막 두께를 갖는 접착 필름을 제조할 수 있다.
Examples of the method for producing the adhesive film for semiconductors are as follows: Each of the above-mentioned components is dissolved in a solvent and sufficiently kneaded using a bead mill. Then, a polyethylene terephthalate (PET ) Film, followed by heating and drying in an oven at 100 ° C for about 10 to 30 minutes to produce an adhesive film having an appropriate film thickness.

상기 반도체용 접착 필름의 두께는 바람직하게는 5 내지 200 ㎛일 수 있고, 보다 바람직하게는 10 내지 100 ㎛ 일 수 있으며, 가장 바람직하게는 15 내지 60 ㎛ 일 수 있다. 상기 접착 필름의 두께가 5 ㎛ 미만일 경우에는 PCB(Printed Circuit Board) 갭-필링(gap-filling) 능력이 부족하여 몰딩 후 보이드 특성이 나빠질 우려가 있으며, 200 ㎛를 초과하는 경우에는 경제성이 떨어지게 된다.
The thickness of the adhesive film for semiconductor may be preferably 5 to 200 mu m, more preferably 10 to 100 mu m, and most preferably 15 to 60 mu m. When the thickness of the adhesive film is less than 5 m, the printed circuit board (GPC) gap-filling ability is insufficient, and the void property after molding is deteriorated. When the thickness exceeds 200 m, the economical efficiency is lowered .

본원 발명의 일 양태에 따르면,According to one aspect of the present invention,

아민 경화제 및 페놀 경화제를 함유하는 반도체용 접착 필름으로서,An adhesive film for semiconductor comprising an amine curing agent and a phenol curing agent,

경화 전 40℃에서의 저장 탄성률(a); 및(A) the storage elastic modulus at 40 占 폚 before curing; And

125℃에서 1시간 및 150℃에서 10분간 경화하는 것을 1 사이클로 했을 때 총 4 사이클 진행 후 170℃에서의 저장 탄성률(b);The storage elastic modulus (b) at 170 캜 after a total cycle of 4 cycles when the curing was performed at 125 캜 for 1 hour and at 150 캜 for 10 minutes as one cycle;

의 비(b/a)가 1.5 내지 3.0인, 반도체용 접착 필름을 제공한다.(B / a) of 1.5 to 3.0.

상기 경화 전 저장 탄성률(a)은, 상기 반도체용 접착 필름을 60℃에서 400 ㎛ 내지 500 ㎛로 라미네이션(lamination)한 후, ARES 장비를 이용하여 승온 속도 50℃/min, 변형률 5%, 프리퀀시 1rad의 조건하에서 측정한, 40℃에서의 모듈러스 값을 의미한다.
The storage elastic modulus (a) before curing was obtained by lamination of the adhesive film for semiconductor from 400 쨉 m to 500 쨉 m at 60 째 C and then heating rate was 50 캜 / min using ARES equipment, strain 5% Quot; means a modulus value measured at 40 ° C under the conditions of

상기 경화 후 저장 탄성률(b)은, 상기 반도체용 접착 필름을 60℃에서 400 ㎛ 내지 500 ㎛로 라미네이션(lamination)한 후 125℃의 오븐에서 1시간, 150℃의 핫 플레이트(hot plate) 위에서 10분간 세미 큐어(Semi cure)하는 것을 1 사이클(cycle)로 하여 총 4 사이클 진행 후, ARES 장비를 이용하여 승온 속도 50℃/min, 변형률 5%, 프리퀀시 1rad의 조건하에서 측정한, 170℃에서의 모듈러스 값을 의미한다.
The storage elastic modulus (b) after curing is measured by lamination of the adhesive film for semiconductor from 400 占 퐉 to 500 占 퐉 at 60 占 폚 and then for 1 hour in an oven at 125 占 폚, Minute, semi-cure was performed for one cycle. After four cycles, the temperature was measured at a temperature rising rate of 50 DEG C / min, a strain of 5% and a frequency of 1 rad using an ARES equipment. Modulus value.

상기 경화 전 및 후의 저장 탄성률의 비(b/a)는 1.5 내지 3.0인 것이 바람직하다. 상기 범위에서 다이 접착 시 보이드 발생 억제 및 EMC 몰딩 시 보이드의 제거 효과를 얻을 수 있고, 경화 후 우수한 전단 강도 및 신뢰성 물성을 얻을 수 있다.
The ratio (b / a) of the storage elastic modulus before and after the curing is preferably 1.5 to 3.0. In the above range, it is possible to obtain an effect of suppressing generation of voids during die bonding and removing voids in EMC molding, and excellent shear strength and reliability properties after curing can be obtained.

본원 발명의 또 다른 일 양태에 따르면, 125℃에서 1시간, 150℃에서 10분 및 175℃에서 1시간 경화 후 전단 강도(Die shear strength)가 9 kgf 이상인, 반도체용 접착 필름을 제공한다. 전단 강도가 9 kgf 이상일 경우 접착제의 도막 강도가 높아 열충격이 가해지는 조건에서도 팽창(swelling)에 따른 불량의 발생을 억제할 수 있어 신뢰성 측면에서 유리하다.
According to another aspect of the present invention, there is provided an adhesive film for a semiconductor having a die shear strength of 9 kgf or more after curing at 125 ° C for 1 hour, 150 ° C for 10 minutes, and 175 ° C for 1 hour. When the shear strength is higher than 9 kgf, the adhesive strength of the adhesive is high, which makes it possible to suppress the occurrence of defects due to swelling even under the condition that thermal shock is applied, which is advantageous in terms of reliability.

상기 경화 후 전단 강도는 두께 720 ㎛의 웨이퍼를 가로 5 mm × 세로 5 mm의 크기로 자른 후 상기 반도체용 접착 필름과 함께 60℃에서 라미네이션하고 접착 부분만 남기고 절단한 다음, 가로 10 mm × 세로 10 mm 크기의 웨이퍼에 가로 5 mm × 세로 5 mm 크기의 상부칩을 올려놓은 후, 120℃ 핫 플레이트 위에서 10 kgf의 힘으로 5초 동안 눌러 붙인 뒤, 125℃의 오븐에서 1시간 세미 큐어를 실시하고, 와이어 본딩 모사 조건인 150℃의 핫 플레이트 위에서 10분간 방치 후 175℃에서 1시간 동안 EMC 경화 조건으로 경화하여, Dyse 4000 설비를 이용하여 100 N bar를 이용하여 10 ㎛ 높이에서 100 mm/s 속도로 측정한, 250℃에서의 전단 강도 값을 의미한다.
After the curing, the wafer having a thickness of 720 μm was cut into a size of 5 mm × 5 mm, laminated at 60 ° C. together with the adhesive film for semiconductor, cut with leaving only the adhesive portion, The upper chip having a size of 5 mm × 5 mm was placed on a wafer having a size of mm, pressed on a hot plate of 120 ° C. for 5 seconds under a force of 10 kgf, and then subjected to a semi-cure in an oven at 125 ° C. for 1 hour , Left on a hot plate at 150 ° C for 10 minutes, and then cured at 175 ° C for 1 hour under EMC curing conditions. Using a Dyse 4000 machine, 100 N bar was used at a speed of 100 mm / s Quot; means the shear strength value at 250 ° C, as measured by the following formula.

본원 발명의 또 다른 일 양태에 따르면, 상기 접착 필름은,According to another aspect of the present invention,

125℃에서 1시간 및 150℃에서 1시간 경화;Curing at 125 캜 for 1 hour and at 150 캜 for 1 hour;

175℃에서 60초간 몰딩(molding); 및Molding at 175 DEG C for 60 seconds; And

175℃에서 1시간 몰드 경화 후의 보이드(void) 면적이,The void area after mold curing at 175 占 폚 for 1 hour,

상기 필름이 부착된 면적을 기준으로 5% 이하인, 반도체용 접착 필름을 제공한다.Wherein the film is not more than 5% based on an area where the film is adhered.

다이 접착면에 보이드가 5% 이상 다량 발생하는 경우 접착 강도가 약해지고 열과 전기 전도성이 저하되게 되며 다이 크랙킹(die cracking)을 유발하는 등, 디바이스의 질과 신뢰성에 악영향을 미칠 수 있기 때문에 5% 이하의 보이드 면적을 갖는 것이 좋다.If voids are formed on the die bonding surface in an amount of 5% or more, the bonding strength is lowered, heat and electric conductivity are lowered, and die cracking is caused, which may adversely affect the quality and reliability of the device. Lt; / RTI >

보이드 면적이 5% 이하라는 것은 수치적으로 0 및 그 미만의 음의 값을 포함하는 의미는 아니며, 상기 보이드 면적의 하한은 0에 근접한 정도의 양의 값으로 한다.
The fact that the void area is 5% or less does not mean that the numerical value includes a negative value of 0 or less, and the lower limit of the void area is a positive value close to zero.

상기 보이드 면적은 상기 접착 필름을 10 mm × 10 mm 커버 글라스와 함께 60℃에서 라미네이션하고 접착 부분만 남기고 절단한 후 PCB에 1 kgf의 힘으로 1초 동안 눌러서 부착한 다음, 125℃에서 1시간 및 150℃에서 1시간 경화 후 EMC(SG-8500B, 제일모직)를 이용하여 175℃에서 60초간 몰딩한 후, 몰드 경화 175℃에서 1시간 진행한 뒤 그라인더(Grinder)로 커버 글라스 위에 덮여있는 몰드를 갈아낸 후 저배율 현미경으로 보이드를 관찰한 것으로, 상기 접착 필름이 부착된 면적을 기준으로 상기 몰딩 후 보이드의 면적을 백분율로 수치화한 값을 의미한다((보이드 면적/접착 필름이 부착된 면적)×100).
The void area was measured by lamination of the adhesive film with a 10 mm x 10 mm cover glass at 60 ° C, cutting with only the adhesive part, pressing on the PCB for 1 second with a force of 1 kgf, After curing at 150 ° C for 1 hour, molding was performed at 175 ° C for 60 seconds using EMC (SG-8500B, Cheil Industries), and then the mold was cured at 175 ° C for 1 hour. Then, the mold covered with a grinder was covered with a grinder Refers to a value obtained by quantifying voids after molding by a percentage based on the area where the adhesive film is adhered (void area / adhered film area) x 100).

본원 발명의 또 다른 일 양태에 따르면,According to another aspect of the present invention,

아민 경화제 및 페놀 경화제를 함유하는 반도체용 접착 필름으로서,An adhesive film for semiconductor comprising an amine curing agent and a phenol curing agent,

125℃에서 1시간, 150℃에서 10분 및 175℃에서 1시간 경화 후 전단 강도가 9 kgf 이상이고,Shear strength after curing at 125 占 폚 for 1 hour, at 150 占 폚 for 10 minutes and at 175 占 폚 for 1 hour,

경화 후 170℃에서의 저장 탄성률이 5.0(106 dyne/cm2) 이상인, 반도체용 접착 필름을 제공한다.And a storage elastic modulus at 170 占 폚 after curing of 5.0 (10 6 dyne / cm 2 ) or more.

5.0(106dyne/cm2) 이상인 경우 170℃에서 몰드 시 가해지는 1톤의 압력을 충분히 버틸 수 있어 칩이 밀리지 않도록 하여 몰드 시 발생될 수 있는 불량을 없앨 수 있다. 또한 전당강도와 내리플로우성이 우수하여 신뢰성에 좋은 영향을 미친다.
If it is 5.0 (10 6 dyne / cm 2 ) or more, the pressure of 1 ton applied at 170 ° C can be sufficiently held to prevent the chip from being pushed, thereby eliminating the defect that may occur during molding. Also, it has excellent strength and low flowability and has a good effect on reliability.

상기 경화 후 저장 탄성률은, 상기 반도체용 접착 필름을 60℃에서 400 ㎛ 내지 500 ㎛로 라미네이션한 후 125℃의 오븐에서 1시간, 150℃의 핫 플레이트 위에서 10분간 세미 큐어하는 것을 1 사이클로 하여 총 4 사이클 진행 후, ARES 장비를 이용하여 승온 속도 50℃/min, 변형률 5%, 프리퀀시 1rad의 조건하에서 측정한, 170℃에서의 모듈러스 값을 의미한다.
The storage elastic modulus after curing was obtained by laminating the adhesive film for semiconductor from 400 占 퐉 to 500 占 퐉 at 60 占 폚 and then semi-curing for 1 hour in an oven at 125 占 폚 for 10 minutes on a hot plate at 150 占 폚. Means a modulus value measured at 170 DEG C under the conditions of a temperature raising rate of 50 DEG C / min, a strain of 5% and a frequency of 1 rad using ARES equipment after the cycle.

본원 발명의 또 다른 일 양태에 따르면, 상기의 반도체용 접착 필름으로 접속된 반도체 장치를 제공한다.According to still another aspect of the present invention, there is provided a semiconductor device connected with the above-mentioned adhesive film for semiconductor.

상기 반도체 장치는, 배선 기판; 상기 배선 기판의 칩 탑재면에 부착되어 있는 반도체용 접착 필름; 및 상기 필름상에 탑재된 반도체 칩을 포함할 수 있다.The semiconductor device includes: a wiring board; An adhesive film for semiconductor attached to the chip mounting surface of the wiring board; And a semiconductor chip mounted on the film.

본원 발명에 사용되는 상기 배선 기판, 반도체 칩은 특별히 한정되지 아니하며, 당해 기술 분야에서 알려진 것을 사용할 수 있다.The wiring board and the semiconductor chip used in the present invention are not particularly limited, and those known in the art can be used.

본원 발명의 반도체 장치를 제조하는 방법은 특별히 한정되지 아니하며, 당해 기술 분야에서 알려진 방법으로 수행될 수 있다.
The method for manufacturing the semiconductor device of the present invention is not particularly limited, and can be performed by a method known in the art.

이하, 실시예, 비교예 및 실험예를 기술함으로써 본원 발명을 보다 상세히 설명한다. 다만, 하기의 실시예, 및 실험예는 본원 발명의 일 예시에 불과하며, 본원 발명의 내용이 이에 한정되는 것으로 해석되어서는 아니된다.
Hereinafter, the present invention will be described in more detail by describing Examples, Comparative Examples and Experimental Examples. However, the following examples and experimental examples are merely examples of the present invention and should not be construed as limiting the scope of the present invention.

실시예Example 1 One

아민 경화제 및 페놀 경화제를 함유하는 반도체용 접착 필름의 제조Preparation of adhesive films for semiconductors containing amine curing agent and phenol curing agent

반도체용 접착 필름의 고형분 100 중량부에 대하여,With respect to 100 parts by weight of the solid content of the adhesive film for semiconductor,

엘라스토머 수지(AD-102S, 제일모직) 67.7 중량부;67.7 parts by weight of an elastomer resin (AD-102S, Cheil Industries);

에폭시 수지(EPPN-502H, 일본 화학) 13.5 중량부;13.5 parts by weight of an epoxy resin (EPPN-502H, Nippon Kagaku);

아민 경화제(DDS, Wako) 7.8 중량부;7.8 parts by weight of an amine curing agent (DDS, Wako);

페놀 경화제(BPA, 국도 화학) 1.5 중량부(수산기 당량: 114 g/eq);Phenol hardener (BPA, Kukdo Chemical Co., Ltd.) 1.5 parts by weight (hydroxyl equivalent: 114 g / eq);

실란 커플링제(S-510, Chisso) 0.5 중량부; 및0.5 parts by weight of a silane coupling agent (S-510, Chisso); And

충진제(R-972, 대구사) 9 중량부를 혼합하여, 유기 용매인 시클로헥사논에 용해시킨 후, 비즈밀을 이용하여 충분히 혼련시킨 다음, 어플리케이터를 이용하여 이형 처리된 폴리에틸렌테레프탈레이트 필름상에 도포하였다. 그 다음 100℃ 오븐에서 20분가량 가열 건조하여 두께 60 ㎛인 반도체용 접착 필름을 제조하였다.
And 9 parts by weight of a filler (R-972, manufactured by Daegu K.K.) were dissolved in cyclohexanone, an organic solvent, and sufficiently kneaded using a bead mill. Then, the mixture was applied onto a polyethylene terephthalate film Respectively. Then, it was heated and dried in an oven at 100 ° C for about 20 minutes to prepare a semiconductor adhesive film having a thickness of 60 μm.

실시예Example 2 2

아민 경화제 및 페놀 경화제를 함유하는 반도체용 접착 필름의 제조Preparation of adhesive films for semiconductors containing amine curing agent and phenol curing agent

반도체용 접착 필름의 고형분 100 중량부에 대하여,With respect to 100 parts by weight of the solid content of the adhesive film for semiconductor,

에폭시 수지(EPPN-502H, 일본 화학)를 12.3 중량부;12.3 parts by weight of an epoxy resin (EPPN-502H, Nippon Chemical);

아민 경화제(DDS, Wako)를 5.5 중량부; 및5.5 parts by weight of amine curing agent (DDS, Wako); And

페놀 경화제(BPA, 국도 화학)를 5.0 중량부로 사용하는 것을 제외하고는 상기 실시예 1과 동일한 방법에 의하여 반도체용 접착 필름을 제조하였다.
An adhesive film for semiconductor was manufactured in the same manner as in Example 1, except that 5.0 parts by weight of a phenol hardener (BPA, Kukdo Chemical Co., Ltd.) was used.

실시예Example 3 3

아민 경화제 및 페놀 경화제를 함유하는 반도체용 접착 필름의 제조Preparation of adhesive films for semiconductors containing amine curing agent and phenol curing agent

반도체용 접착 필름의 고형분 100 중량부에 대하여,With respect to 100 parts by weight of the solid content of the adhesive film for semiconductor,

에폭시 수지(EPPN-502H, 일본 화학)를 11.7 중량부;11.7 parts by weight of an epoxy resin (EPPN-502H, Nippon Chemical);

아민 경화제(DDS, Wako)를 3.9 중량부; 및3.9 parts by weight of an amine curing agent (DDS, Wako); And

페놀 경화제(BPA, 국도 화학)를 7.2 중량부로 사용하는 것을 제외하고는 상기 실시예 1과 동일한 방법에 의하여 반도체용 접착 필름을 제조하였다.
An adhesive film for semiconductor was manufactured in the same manner as in Example 1, except that 7.2 parts by weight of a phenol curing agent (BPA, Kukdo Chemical Co., Ltd.) was used.

비교예Comparative Example 1 One

경화제로서 아민 경화제만을 단독으로 함유하는 반도체용 접착 필름의 제조Production of an adhesive film for semiconductors containing only an amine curing agent as a curing agent

반도체용 접착 필름의 고형분 100 중량부에 대하여,With respect to 100 parts by weight of the solid content of the adhesive film for semiconductor,

에폭시 수지(EPPN-502H, 일본 화학)를 13.8 중량부;13.8 parts by weight of an epoxy resin (EPPN-502H, Nippon Chemical);

아민 경화제(DDS, Wako)를 9 중량부 사용하고;9 parts by weight of an amine curing agent (DDS, Wako) was used;

페놀 경화제를 사용하지 않는 것을 제외하고는 상기 실시예 1과 동일한 방법에 의하여 반도체용 접착 필름을 제조하였다.
An adhesive film for semiconductor was manufactured in the same manner as in Example 1, except that a phenol curing agent was not used.

비교예Comparative Example 2 2

경화제로서 페놀 경화제만을 단독으로 함유하는 반도체용 접착 필름의 제조Production of adhesive film for semiconductor containing solely phenol curing agent as a curing agent

반도체용 접착 필름의 고형분 100 중량부에 대하여,With respect to 100 parts by weight of the solid content of the adhesive film for semiconductor,

에폭시 수지(EPPN-502H, 일본 화학)를 10.1 중량부;10.1 parts by weight of an epoxy resin (EPPN-502H, Nippon Chemical);

페놀 경화제(BPA, 국도 화학)를 12.7 중량부 사용하고;12.7 parts by weight of a phenol hardener (BPA, Kukdo Chemical) was used;

아민 경화제를 사용하지 않는 것을 제외하고는 상기 실시예 1과 동일한 방법에 의하여 반도체용 접착 필름을 제조하였다.
An adhesive film for semiconductor was manufactured in the same manner as in Example 1 except that the amine curing agent was not used.

비교예Comparative Example 3 3

아민 경화제 및 페놀 경화제를 함유하는 반도체용 접착 필름의 제조Preparation of adhesive films for semiconductors containing amine curing agent and phenol curing agent

반도체용 접착 필름의 고형분 100 중량부에 대하여,With respect to 100 parts by weight of the solid content of the adhesive film for semiconductor,

에폭시 수지(EPPN-502H, 일본 화학)를 11.1 중량부;11.1 parts by weight of an epoxy resin (EPPN-502H, Nippon Kagaku);

아민 경화제(DDS, Wako)를 2.5 중량부; 및2.5 parts by weight of amine curing agent (DDS, Wako); And

페놀 경화제(BPA, 국도 화학)를 9.2 중량부 사용하는 것을 제외하고는 실시예 1과 동일한 방법에 의하여 반도체용 접착 필름을 제조하였다.
An adhesive film for semiconductor was manufactured in the same manner as in Example 1, except that 9.2 parts by weight of a phenol hardener (BPA, Kukdo Chemical Co., Ltd.) was used.

하기 표 1은 상기 실시예 1 내지 3 및 비교예 1 내지 3의 접착 필름의 조성을 중량부로 나타낸 것이다.Table 1 below shows the compositions of the adhesive films of Examples 1 to 3 and Comparative Examples 1 to 3 in parts by weight.

실시예Example 1 One 실시예Example 2 2 실시예Example 3 3 비교예Comparative Example 1 One 비교예Comparative Example 2 2 비교예Comparative Example 3 3 엘라스토머 수지Elastomer resin 67.767.7 67.767.7 67.767.7 67.767.7 67.767.7 67.767.7 에폭시 수지Epoxy resin 13.513.5 12.312.3 11.711.7 13.813.8 10.110.1 11.111.1 아민 경화제Amine curing agent 7.87.8 5.55.5 3.93.9 99 -- 2.52.5 페놀 경화제Phenol hardener 1.51.5 55 7.27.2 -- 12.712.7 9.29.2 실란Silane 커플링제Coupling agent 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 충진제Filler 99 99 99 99 99 99 중량부Weight portion 합계 Sum 100100 100100 100100 100100 100100 100100

실험예Experimental Example 1 One

경화 전 저장 탄성률의 측정Measurement of storage modulus before curing

상기 반도체용 접착 필름을 60℃에서 400 ㎛ 내지 500 ㎛로 라미네이션(lamination)한 후, ARES 장비를 이용하여 승온 속도 50℃/min, 변형률 5%, 프리퀀시 1rad의 조건하에서 측정하여, 40℃에서의 모듈러스 값을 구하였다.
The semiconductor adhesive film was laminated at a temperature of 60 占 폚 to 400 占 퐉 to 500 占 퐉 and then measured under the conditions of a temperature raising rate of 50 占 폚 / min, a strain rate of 5% and a frequency of 1 rad using ARES equipment, The modulus values were obtained.

실험예Experimental Example 2 2

경화 후 저장 탄성률의 측정Measurement of storage modulus after curing

상기 실시예 1 내지 3 및 비교예 1 내지 3에 의하여 제조된 각각의 접착 필름을 60℃에서 450 ㎛로 라미네이센한 후 125℃ 오븐에서 1시간 및 150℃ 핫 플레이트 위에서 10분간 세미 큐어하는 것을 1 사이클로하여 총 4 사이클 진행 후, ARES 장비를 이용하여 승온 속도 50℃/min, 변형률 5%, 프리퀀시 1rad인 조건에서 측정하여, 170℃에서의 모듈러스 값을 구하였다.
Each of the adhesive films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 was laminated to 450 탆 at 60 캜 and then semicured in an oven at 125 캜 for 1 hour and a 150 캜 hot plate for 10 minutes 1 cycle, and the modulus was measured at 170 DEG C under the conditions of a heating rate of 50 DEG C / min, a strain of 5% and a frequency of 1 rad using ARES equipment.

실험예Experimental Example 3 3

몰딩 후 After molding 보이드Boyd 상태의 관찰 Observation of status

가로 10 mm × 세로 10 mm 크기의 커버 글라스에 상기 실시예 1 내지 3 및 비교예 1 내지 3에 의하여 제조된 각각의 접착 필름을 함께 60℃에서 라미네이션한 후, PCB에 1 kgf의 힘으로 1초간 눌러 붙인 후 125℃에서 1시간 및 150℃에서 1시간 동안 큐어를 실시한 다음, EMC(SG-8500B, 제일모직)를 이용하여 175℃에서 60초간 몰딩한 후 175℃에서 1시간 동안 몰드 경화를 하였다. 그 다음, 이것을 폴리셔(Polisher)를 이용하여 폴리싱한 후 보이드 상태를 관찰하였다. 상기 접착 필름이 부착된 면적을 기준으로하여 눈금 격자표를 이용해 남아있는 보이드 면적이 5% 이하일 경우 매우 양호, 5% 초과 10% 미만일 경우는 양호, 10%를 초과하는 경우에는 불량으로 평가하였다.
Each of the adhesive films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 was laminated together at 60 DEG C on a cover glass having a size of 10 mm x 10 mm in size, Cured for 1 hour at 125 ° C and 1 hour at 150 ° C, molded at 175 ° C for 60 seconds using EMC (SG-8500B, Cheil Industries), and cured at 175 ° C for 1 hour . Then, this was polished using a polisher and the void state was observed. When the remaining void area was less than 5%, it was evaluated as good, more than 5% was less than 10%, and when it exceeded 10%, it was evaluated as defective.

실험예Experimental Example 4 4

경화 후 전단 강도(Shear Strength after Curing ( DieDie shearshear strengthstrength )의 측정)

이산화막으로 코팅되어 있는 두께 720 ㎛의 웨이퍼를 사용하여 가로 5 mm × 세로 5 mm의 크기로 자른 후 상기 실시예 1 내지 3 및 비교예 1 내지 3에 의하여 제조된 각각의 접착 필름과 함께 60℃에서 라미네이션한 다음, 접착 부분만을 남기고 절단하였다. 그 다음, 가로 10 mm × 세로 10 mm 크기의 웨이퍼에 가로 5 mm × 세로 5 mm 크기의 상부칩을 올려놓은 후, 120℃ 핫 플레이트 위에서 10 kgf의 힘으로 5초 동안 눌러 붙인 뒤 125℃의 오븐에서 1시간, 150℃의 핫 플레이트 위에서 10분간 경화, 125℃에서 1시간, 150℃에서 10분 및 175℃에서 1시간 경화의 2가지 조건에서 경화를 실시한 다음, Dyse 4000 설비를 이용하여 100 N bar, 10 ㎛ 높이에서 100 mm/s 속도로 250℃에서의 전단 강도 값을 측정하였다.
Cut into a size of 5 mm in width and 5 mm in width using a wafer having a thickness of 720 탆 coated with a SiO 2 film and then laminated together with the respective adhesive films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 at 60 ° C And then cut with leaving only the adhesive portion. Then, an upper chip having a size of 5 mm × 5 mm was placed on a wafer having a size of 10 mm × 10 mm. The wafer was pressed on a 120 ° C. hot plate with a force of 10 kgf for 5 seconds, , Curing for 1 hour on a hot plate at 150 ° C for 10 minutes, curing at 125 ° C for 1 hour, curing at 150 ° C for 10 minutes, and curing at 175 ° C for 1 hour, followed by 100 N bar, shear strength values at 250 캜 at a height of 10 탆 and a speed of 100 mm / s were measured.

실험예Experimental Example 5 5

내리플로우성Down flow 평가 evaluation

가로 10 mm × 세로 10 mm 크기의 이산화막으로 코팅되어있는 두께 150 ㎛의 웨이퍼에 상기 실시예 1 내지 3 및 비교예 1 내지 3에 의하여 제조된 각각의 접착 필름을 마운팅한 후, PCB에 1 kgf의 힘으로 1초간 눌러 붙인 후 125℃에서 1시간 및 150℃에서 1시간 큐어를 실시한 다음, EMC(SG-8500B, 제일모직)를 이용하여 175℃에서 60초간 몰딩한 후, 175℃에서 1시간 동안 후경화를 실시하였다. 상기 후경화를 실시한 후 온도 85℃, 상대 습도 85%의 항온ㆍ항습 챔버(chamber)를이용하여 4시간 동안 흡습시킨 다음, 최고 온도 260℃의 IR 리플로우를 3회 통과시킨 후 SAT(Sonix quantum 350)설비의 t-scan 기법을 이용하여 비파괴 검사법으로 박리 여부를 확인하였다. 박리가 발생하면 불량, 발생하지 않으면 양호로 평가하였다.
Each of the adhesive films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 was mounted on a 150 μm thick wafer coated with a SiO 2 film having a size of 10 mm × 10 mm, and 1 kgf And then cured at 125 ° C for 1 hour and at 150 ° C for 1 hour. Then, molding was performed at 175 ° C for 60 seconds using EMC (SG-8500B, Cheil Industries) Lt; / RTI > After the post-curing, the film was subjected to moisture absorption for 4 hours using a constant temperature and humidity chamber having a temperature of 85 ° C. and a relative humidity of 85%. The film was then subjected to IR reflow at a maximum temperature of 260 ° C. three times, 350) t-scan technique was used to confirm the detachment by non-destructive testing. Defective when peeling occurred, and evaluated as good when peeling occurred.

하기의 표 2는 상기 실시예 1 내지 3 및 비교예 1 내지 3에 의하여 제조된 접착 필름의 아민 경화제/페놀 경화제의 몰%비, 및 상기 실험예 1 내지 5의 측정 결과를 나타낸 것이다.The following Table 2 shows the molar ratio of the amine curing agent / phenol curing agent of the adhesive films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 and the measurement results of Experimental Examples 1 to 5.

실시예Example 1 One 실시예Example 2 2 실시예Example 3 3 아민/페놀 경화제의 몰%비Mol% ratio of amine / phenol curing agent 5.1≒(67.2/13.18)5.1? (67.2 / 13.18) 0.5≒(33.3/66.7)0.5? (33.3 / 66.7) 0.33≒(25/75)0.33? (25/75) 저장 탄성률Storage modulus
(10(10 66 dynedyne // cmcm 22 )) 경화 전(40℃)Before curing (40 ° C) 4.914.91 4.744.74 4.504.50 경화 후(170℃)After curing (170 ° C) 10.110.1 8.38.3 7.17.1 보이드Boyd 매우 양호Very good 매우 양호Very good 양호Good 전당 강도(Full strength ( kgfkgf )) 12.8512.85 11.0811.08 10.7410.74 내리플로우성Down flow 양호Good 양호Good 양호Good

비교예Comparative Example 1 One 비교예Comparative Example 2 2 비교예Comparative Example 3 3 아민/페놀 경화제의 몰%비Mol% ratio of amine / phenol curing agent 아민 100%Amine 100% 페놀 100%Phenol 100% 0.17≒(14.3/85.7)0.17? (14.3 / 85.7) 저장 탄성률Storage modulus
(10(10 66 dynedyne // cmcm 22 )) 경화 전(40℃)Before curing (40 ° C) 4.344.34 3.263.26 4.074.07 경화 후(170℃)After curing (170 ° C) 2.632.63 2.302.30 4.94.9 보이드Boyd 불량Bad 불량Bad 양호Good 전당 강도(Full strength ( kgfkgf )) 5.825.82 0.930.93 8.828.82 내리플로우성Down flow 불량Bad 불량Bad 불량Bad

상기 실시예 1 내지 3과 비교예 1 및 2를 비교해 보면, 아민 경화제와 페놀 경화제를 함께 사용한 경우에 경화 전과 후의 저장 탄성률의 차이가 큰 것으로 확인 되었다. 또한 아민 경화제와 페놀 경화제를 함께 사용한 경우에 보이드 특성이 매우 양호하게 나타났으며, 경화 후 저장 탄성률이 높아 우수한 전단 강도 및 내리플로우성을 나타내는 것으로 확인되었다.Comparing Examples 1 to 3 and Comparative Examples 1 and 2, it was confirmed that when the amine curing agent and the phenol curing agent were used together, there was a large difference in storage modulus before and after curing. In addition, when the amine curing agent and the phenol curing agent were used together, the void characteristics were very good and the storage modulus after curing was high, indicating excellent shear strength and bottom flowability.

한편, 실시예 1 내지 3 및 비교예 3을 비교한 결과, 페놀 경화제(x)에 대한 아민 경화제(y)의 몰%비(y/x)가 0.3 미만인 경우에는 목적하는 만큼의 경화 전, 후의 저장 탄성률의 변화를 달성할 수 없음을 확인할 수 있었다. 또한, 몰%비가 0.3 미만인 경우에는 보이드 특성은 양호하나, 경화 후의 저장 탄성률이 낮아 전단 강도 및 내리플로우성에 있어서 불량인 것으로 평가되었다.On the other hand, when Examples 1 to 3 and Comparative Example 3 were compared, it was found that when the molar ratio (y / x) of the amine curing agent (y) to the phenol curing agent (x) was less than 0.3, It was confirmed that the change of the storage elastic modulus can not be achieved. Further, when the mol% ratio was less than 0.3, the void property was good, but the storage elastic modulus after curing was low, and it was evaluated to be poor in shear strength and bottom flowability.

Claims (17)

아민 경화제 및 페놀 경화제를 함유하는 반도체용 접착 필름으로서,
경화 전 40℃에서의 저장 탄성률(a); 및
80% 경화 후 170℃에서의 저장 탄성률(b);
의 비(b/a)가 1.5 내지 3.0이고,
125℃에서 1시간, 150℃에서 10분 및 175℃에서 1시간 경화 후의 전단 강도(Die shear strength)가 9 kgf 이상인, 반도체용 접착 필름.An adhesive film for semiconductor comprising an amine curing agent and a phenol curing agent,
(A) the storage elastic modulus at 40 占 폚 before curing; And
(B) storage elastic modulus at 170 占 폚 after 80% curing;
(B / a) of from 1.5 to 3.0,
Wherein the film has a shear strength of 9 kgf or more after curing at 125 占 폚 for 1 hour, at 150 占 폚 for 10 minutes, and at 175 占 폚 for 1 hour. 제1항에 있어서, 상기 아민 경화제가 디아미노 디페닐 설폰(Diamino diphenyl sulfone)인, 반도체용 접착 필름.The adhesive film for semiconductor according to claim 1, wherein the amine curing agent is diamino diphenyl sulfone. 제1항에 있어서, 상기 페놀 경화제가 비스페놀 A 또는 비스페놀 F인, 반도체용 접착 필름.The adhesive film for semiconductor according to claim 1, wherein the phenol hardener is bisphenol A or bisphenol F. 삭제delete 제1항 내지 제3항 중 어느 하나의 항에 있어서,
125℃에서 1시간 및 150℃에서 1시간 경화; 및
175℃에서 60초간 몰딩(molding)한 후 175℃에서 1시간 몰드 경화 후의 보이드(void) 면적이,
상기 필름이 부착된 면적을 기준으로 5% 이하인, 반도체용 접착 필름.4. The method according to any one of claims 1 to 3,
Curing at 125 캜 for 1 hour and at 150 캜 for 1 hour; And
After molding at 175 DEG C for 60 seconds, the void area after the mold curing at 175 DEG C for 1 hour,
Wherein the film is not more than 5% based on the area of the film. 아민 경화제 및 페놀 경화제를 함유하는 반도체용 접착 필름으로서,
125℃에서 1시간, 150℃에서 10분 및 175℃에서 1시간 경화 후 전단 강도가 9 kgf 이상이고,
80% 경화 후 170℃에서의 저장 탄성률이 5.0(106 dyne/cm2) 이상인, 반도체용 접착 필름.An adhesive film for semiconductor comprising an amine curing agent and a phenol curing agent,
Shear strength after curing at 125 占 폚 for 1 hour, at 150 占 폚 for 10 minutes and at 175 占 폚 for 1 hour,
80% of the storage modulus of the cured after 170 ℃ 5.0 (10 6 dyne / cm 2) or more, the adhesive film for a semiconductor. 제6항에 있어서,
125℃에서 1시간 및 150℃에서 1시간 경화; 및
175℃에서 60초간 몰딩(molding)한 후 175℃에서 1시간 몰드 경화 후의 보이드(void) 면적이,
상기 필름이 부착된 면적을 기준으로 5% 이하인, 반도체용 접착 필름.The method according to claim 6,
Curing at 125 캜 for 1 hour and at 150 캜 for 1 hour; And
After molding at 175 DEG C for 60 seconds, the void area after the mold curing at 175 DEG C for 1 hour,
Wherein the film is not more than 5% based on the area of the film. 제6항 또는 제7항에 있어서, 상기 아민 경화제가 디아미노 디페닐 설폰인, 반도체용 접착 필름.The adhesive film for semiconductor according to claim 6 or 7, wherein the amine curing agent is diamino diphenyl sulfone. 제6항 또는 제7항에 있어서, 상기 페놀 경화제가 비스페놀 A 또는 비스페놀 F인, 반도체용 접착 필름.The adhesive film for semiconductor according to claim 6 or 7, wherein the phenol hardener is bisphenol A or bisphenol F. a) 바인더 수지;
b) 에폭시 수지;
c) 충진제;
d) 아민 경화제; 및
e) 페놀 경화제를 함유하는 반도체용 접착 필름에 있어서,
상기 페놀 경화제(x)에 대한, 상기 아민 경화제(y)의 몰%비(y/x)가 0.3 내지 10인, 반도체용 접착 필름.a) a binder resin;
b) an epoxy resin;
c) fillers;
d) amine curing agents; And
e) an adhesive film for semiconductor containing a phenol curing agent,
Wherein a mol% ratio (y / x) of the amine curing agent (y) to the phenol curing agent (x) is 0.3 to 10. 제10항에 있어서,
경화 전 40℃에서의 저장 탄성률(a); 및
80% 경화 후 170℃에서의 저장 탄성률(b);
의 비(b/a)가 1.5 내지 3.0인, 반도체용 접착 필름.11. The method of claim 10,
(A) the storage elastic modulus at 40 占 폚 before curing; And
(B) storage elastic modulus at 170 占 폚 after 80% curing;
(B / a) of 1.5 to 3.0. 제10항에 있어서, 상기 필름은, 125℃에서 1시간, 150℃에서 10분 및 175℃에서 1시간 경화 후 전단 강도(Die shear strength)가 9 kgf 이상인, 반도체용 접착 필름.The adhesive film for semiconductor according to claim 10, wherein the film has a shear strength of 9 kgf or more after curing at 125 ° C for 1 hour, at 150 ° C for 10 minutes, and at 175 ° C for 1 hour. 제6항에 있어서, 상기 필름의 고형분 100 중량부에 대하여,
a) 바인더 수지 40 내지 80 중량부;
b) 에폭시 수지 1 내지 30 중량부;
c) 충진제 1 내지 30 중량부;
d) 아민 경화제 0.1 내지 20 중량부; 및
e) 페놀 경화제 0.1 내지 20 중량부
를 함유하는, 반도체용 접착 필름.The film according to claim 6, wherein, based on 100 parts by weight of the solid content of the film,
a) 40 to 80 parts by weight of a binder resin;
b) 1 to 30 parts by weight of an epoxy resin;
c) 1 to 30 parts by weight of a filler;
d) 0.1 to 20 parts by weight of an amine curing agent; And
e) 0.1 to 20 parts by weight of phenol curing agent
By weight based on the total weight of the adhesive layer. 제10항에 있어서, 상기 바인더 수지가 엘라스토머 수지인, 반도체용 접착 필름.The adhesive film for semiconductor according to claim 10, wherein the binder resin is an elastomer resin. 제10항에 있어서, 상기 아민 경화제가 디아미노 디페닐 설폰인, 반도체용 접착 필름.The adhesive film for semiconductor according to claim 10, wherein the amine curing agent is diamino diphenyl sulfone. 제10항 내지 제15항 중 어느 하나의 항에 있어서, 상기 페놀 경화제가 비스페놀 A 또는 비스페놀 F인, 반도체용 접착 필름.The adhesive film for semiconductor according to any one of claims 10 to 15, wherein the phenol hardener is bisphenol A or bisphenol F. a) 배선 기판;
b) 상기 배선 기판의 칩 탑재면에 부착되어 있는 반도체용 접착 필름; 및
c) 상기 반도체용 접착 필름상에 탑재된 반도체 칩
을 포함하는 반도체 장치로서,
상기 반도체용 접착 필름은 제1항, 제6항 및 제10항 중 어느 하나의 항에 기재된 필름인, 반도체 장치.a) a wiring board;
b) an adhesive film for semiconductor attached to the chip mounting surface of the wiring board; And
c) a semiconductor chip mounted on the adhesive film for semiconductor,
A semiconductor device comprising:
Wherein the semiconductor adhesive film is the film according to any one of claims 1, 6, and 10.
KR1020110136327A 2011-12-16 2011-12-16 Adhesive film for semiconductor KR101395707B1 (en)

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KR101936217B1 (en) * 2017-06-16 2019-01-08 (주)이녹스첨단소재 FOD adhesive film of semiconductor controller embedding type and Semiconductor package
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US9169425B2 (en) 2015-10-27
KR20130068889A (en) 2013-06-26

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